Substituted 2-amino-5-maleimido thiophenes and substituted 2-amino-maleimido thiazoles

ABSTRACT

Provided are certain substituted 2-aminothiazoles and 2-aminothiophenes which are useful as red colorants and as intermediates in the synthesis of bathochromic azo dyes. These compounds are prepared by reacting 2-aminothiophenes or 2-aminothiazoles, which contain a primary amino group, with 2-chloro-3-negatively-substituted maleimides. These compounds can be diazotized and coupled with azo components, for example, anilines, 1,2,3,4-tetrahydroquinolines, 2,3-dihydroindoles, and 3,4-dihydro-2H-1,4-benzoxazines to form bathochromic blue-cyan azo dyes.

FIELD OF THE INVENTION

This invention belongs to the field of organic chemistry. More particularly, it relates to substituted 2-aminothiophenes, 2-aminothiazoles, and bathochromic azo colorants prepared therefrom.

BACKGROUND OF THE INVENTION

Various synthetic methods are available for preparing negatively substituted 2-aminothiophenes and 2-aminothiazoles, which are useful as intermediates for preparing azo dyes for textile fibers. (See, for example, Weaver and Shuttleworth, Dyes and Pigments, 3, 81-121 (1982).) Many Of these procedures are complicated and laborious, with accompanying low yields. Often, the starting materials needed are not readily available and are expensive, thus rendering the desired negatively substituted 2-aminothiophenes and 2-aminothiazoles prohibitively expensive. Normally, to produce the most bathochromic colorants when diazotized and coupled, the 2-aminothiophenes must have negative groups in the 2,5-positions. These intermediate compounds are usually essentially colorless or are pale yellow in color as are the negatively substituted 2-aminothiazoles. Various colors from yellow to cyan can be produced by diazotizing and coupling the diazonium salts thus produced with appropriate couplers. It is very desirable to produce bathochromic blue shades and these are normally only possible when two very strongly electron withdrawing groups are in positions 2 and 5 of the intermediate thiophenes. None of these known intermediate negatively substituted 2-aminothiophenes or 2-aminothiazoles are useful as colorants.

It is known that 2-chloro-3-cyanomaleimide reacts with primary aromatic amines such as aniline to replace one of the hydrogens attached to the nitrogen, e.g. aniline reacts to give 2-anilino-3-cyanomaleimide. (Wiley et al., J. Am. Chem. Soc., 80, 138528 (1958)). ##STR1##

The compound thus produced has no significant color and has no utility as a colorant. Furthermore, since it has no primary amine present, the compound cannot be diazotized to produce a diazonium salt which is capable of being coupled to produce valuable azo colorants.

It is not expected, based on the prior art, that 2-aminothiophenes and 2-aminothiazoles, which contain primary amine groups, would react with 2-chloro-3-negatively substituted maleimides to give 5-negatively substituted 2-aminothiophenes and 2-aminothiazoles compounds useful as colorants and which have free primary amine groups capable of being diazotized to produce bathochromic azo dyes.

Various electron rich compounds are known to react with 2-chloro-3-cyanomaleimide to give colorants useful as colorants for textile fibers, but none have primary amine groups capable of being diazotized; no 2-aminothiophenes or 2-aminothiazoles are reacted. (See, for example, U.S. Pat. No. 3,096,339).

SUMMARY OF THE INVENTION

The present invention provides various substituted 2-aminothiazoles and thiophenes which are useful as intermediates in the synthesis of bathochromic azo dyes.

These intermediates can then be diazotized and coupled with azo components, for example, anilines, 1,2,3,4-tetrahydroquinolines, 2,3-dihydroindoles, and 3,4-dihydro-2H-1,4-benzoxazines.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides compounds of Formula (I): ##STR2## wherein R is hydrogen, C₁ -C₈ alkyl, C₁ -C₈ substituted alkyl, C₃ -C₈ alkenyl, C₃ -C₈ alkynyl, C₅ -C₇ cycloalkyl, C₅ -C₈ substituted cycloalkyl, phenyl, or substituted phenyl;

X is cyano, C₁ -C₈ alkylsulfonyl, phenylsulfonyl, or substituted phenylsulfonyl;

Y is hydrogen, C₁ -C₄ alkyl, C₅ -C₇ cycloalkyl, halogen, phenyl, substituted phenyl, 2-thienyl, 2-thienyl substituted with one or two halogen, C₁ -C₄ alkyl, or C₁ -C₄ alkoxy, or Y is 2-furanyl;

Z is nitrogen or a group of the formula --C(R₁)═, wherein R₁ is cyano, --CO₂ R₂, --COR₃, --CONHR₂, or --SO₂ R₃, wherein R₂ is hydrogen, C₁ -C₈ alkyl, C₁ -C₈ substituted alkyl, C₅ -C₇ cycloalkyl, C₃ -C₈ alkenyl, phenyl, or substituted phenyl, and R₃ is C₁ -C₈ alkyl, phenyl, or substituted phenyl.

The utility of negatively substituted 2-aminothiazoles and 2-aminothiophenes for producing bathochromic azo dyes by diazotization and coupling of the diazonium salts thus produced with aromatic amines is known, but preparation of the intermediate amines requires complicated, laborious and expensive synthetic methods. In many cases the yields are low and multi-steps synthetic routes are involved. (See, for example, John Griffiths, Colour and Constitution of Organic Molecules, Academic Press, London, 1976, p. 186; John Griffiths, editor, Development in the Chemistry and Technology of Organic Dyes, Blackwell Scientific Publications, Oxford, 1984, pages 11-13; and P. F. Gordon and P. Gregory, Organic Chemistry in Colour, Springer-Verlag, New York, 1983, page 130.)

In contrast, the negatively substituted 2-aminothiazoles and 2-aminothiophenes of this invention are prepared in high yields and in a one step reaction by reacting readily available 2-aminothiazoles and 2-aminothiophenes with maleimide compounds which contain as substitutents a reactive halogen in the 2-position and a negative groups, e.g., cyano, in the 3-position. For example, the available 2-aminothiazoles and 2-aminothiophenes of Formula (II) are reacted with 2-chloro-3-cyanomaleimide according to the following scheme: ##STR3##

Inert solvents such as esters, e.g., ethyl acetate; halogenated hydrocarbons, e.g., methylene chloride; ketones, e.g., acetone and carboxamides, e.g., N,N-dimethylformamide may be used. The reaction temperatures typically vary between room temperature and about 100° C.

In another synthetic route, (E. L. Martin et al., J. Org. Chem., 26, 2032 (1961), 2,3-dichloromaleimides are reacted with the intermediate 2-aminothiazoles and 2-aminothiophenes in the presence of metal cyanides, e.g., sodium cyanide or metal sulfinates, e.g., p-toluenesulfinic acid, Na salt to give compounds of Formula I. ##STR4##

Compounds of Formula I may be used to color textile fibers red shades, but their primary utility is to provide bathochromic blue→cyan azo colorants III upon diazotization and coupling with azo components (C) selected from anilines, 1,2,3,4-tetrahydroquinolines, 2,3-dihydroindoles ##STR5## and 3,4-dihydro-2H-1,4-benzoxazines (benzomorpholines). Thus, as a further aspect of the present invention there is provided compounds of Formula (III). Especially preferred are those compounds where C is selected from the following formulae: ##STR6## wherein: R₄ is hydrogen or 1-2 groups selected from C₁ -C₄ alkyl, C₁ -C₄ alkoxy, halogen, NHCOR₂, NHSO₂ R₃, NHCO₂ R₃ or NHCONHR₂, wherein R₂ and R₃ are as defined previously;

R₅ and R₆ are selected from hydrogen, unsubstituted and substituted C₁ -C₈ alkyl, C₃ -C₈ alkenyl, C₃ -C₈ alkynyl, unsubstituted and substituted C₅ -C₇ cycloalkyl and unsubstituted and substituted phenyl. Also, R₅ and R₆ may be combined with the nitrogen to which they are attached to form a radical having the formula ##STR7## wherein X₁ is selected from --CH₂ --, --O--, --S--, --SO₂ --, --CO--, --CO₂ --, --NH--, --N--COC₁ --C₄ alkyl or --N--SO₂ C₁ -C₄ alkyl.

R₇, R₈ and R₉ are hydrogen or C₁ -C₄ alkyl.

The C₁ -C₈ unsubstituted are substituted alkyl groups represented by R, R₂ and R₃ include straight or branched chain fully saturated hydrocarbon radicals and these substituted with at least one substituent selected from halogen, hydroxy, C₁ -C₆ alkoxy, C₁ -C₆ alkanoyloxy, C₅ -C₆ cycloalkyl, cyano, C₁ -C₆ carbalkoxy, phenyl or substituted phenyl and phenoxy or substituted phenoxy.

C₁ -C₆ unsubstituted and substituted alkyl groups represented by R₅ and R₆ include straight or branched chain fully saturated hydrocarbon radicals and these substituted with one or more of the following: C₅ -C₇ cycloalkyl and C₅ -C₇ cycloalkyl substituted with one or two of C₁ -C₆ alkyl, C₁ -C₆ alkoxy or halogen; phenyl and phenyl substituted with one or two of C₁ -C₆ alkyl, C₁ -C₆ alkoxy, C₁ -C₆ alkoxycarbonyl, halogen, C₁ -C₆ alkanoylamino, cyano, nitro or C₁ -C₆ alkylsulfonyl; cyano; hydroxy; halogen; 2-pyrrolidino; phthalimidino; vinylsulfonyl; acrylamido; o-benzoic sulfimido; C₁ -C₆ alkoxy; C₁ -C₆ alkoxy-C₁ -C₆ alkoxy; cyano C₁ -C₆ alkoxy; hydroxy C₁ -C₆ alkoxy; phenoxy; phenoxy substituted with C₁ -C₆ alkyl, C₁ -C₆ alkoxy, or halogen; groups of the formulae: ##STR8## wherein

Y¹ is selected from o-phenylene; o-phenylene substituted with C₁ -C₆ alkyl, C₁ -C₆ alkoxy, halogen or nitro; C₂ -C₃ alkylene; --O--CH₂ --; --OCH₂ CH₂ --; --CH₂ OCH₂ --; --S--CH₂ --; --CH₂ SCH₂ --; --NHCH₂ --; --NHCH₂ CH₂ --; --N(alkyl)CH₂ --; --N(alkyl)CH₂ CH₂ -- or --NHC(C₆ H₅)₂ --; groups of the formulae: ##STR9## wherein

R₁₀ is selected from C₁ -C₆ alkyl; C₅ -C₇ cycloalkyl; phenyl; phenyl substituted with one or more groups selected from C₁ -C₆ alkyl, C₁ -C₆ alkoxy or halogen; pyridyl, pyrimidinyl; benzoxazolyl; benzothiazolyl; benzimidazolyl; 1,3,4-thiadiazolyl, 1,3,4-oxadiazolyl; these heterocyclic radicals substituted with one or more groups selected from C₁ -C₆ alkyl, C₁ -C₆ alkoxy or halogen; wherein R₁₁ is selected from hydrogen, lower alkyl or benzyl; groups of the formulae:

    --SO.sub.2 R.sub.12 ; --SO.sub.2 N(R.sub.13)R.sub.14 ; --CON(R.sub.13)R.sub.14 ; N(R.sub.13)COR.sub.14 ;

    OCOR.sub.13 ; OCO.sub.2 R.sub.13 ; OCON(R.sub.13)R.sub.14

wherein

R₁₂ is selected from C₅ -C₇ cycloalkyl; C₅ -C₇ cycloalkyl substituted with C₁ -C₆ alkyl; allyl; phenyl; phenyl substituted with one or two groups selected from C₁ -C₆ alkyl, C₁ -C₆ alkoxy or halogen; C₁ -C₆ alkyl; C₁ -C₆ alkyl substituted with one or more groups selected from C₁ -C₆ alkoxy, halogen, cyano, C₅ -C₇ cycloalkyl, phenyl, phenoxy, C₁ -C₆ alkylthio or C₁ -C₆ alkylsulfonyl; R₁₃ and R₁₄ are each independently selected from hydrogen or those groups represented by R₁₂.

In the terms C₁ -C₆ alkyl, C₁ -C₆ alkoxy, C₁ -C₆ alkanoyloxy, C₁ -C₆ alkoxycarbonyl, C₁ -C₆ alkylsulfonyl, and C₁ -C₆ alkylthio, the alkyl portion of the moiety is a fully saturated straight or branched chain hydrocarbon radical having from one to six carbons.

The unsubstituted and substituted C₅ -C₇ cycloalkyl groups mentioned above refer to cycloaliphatic hydrocarbon groups which contain 5 to 7 carbons in the ring and these cycloalkyl groups substituted with one or two of C₁ -C₄ alkyl, C₁ -C₄ alkoxy, hydroxy or C₁ -C₄ alkanoyloxy.

The substituted phenyl groups mentioned above, unless otherwise specified, represent such phenyl groups substituted by one or two of C₁ -C₆ alkyl, C₁ -C₆ alkoxy, C₁ -C₆ alkoxycarbonyl, C₁ -C₆ alkanoyloxy, C₁ -C₆ alkanoylamino, halogen, cyano, C₁ -C₆ alkylsulfonyl or hydroxy.

The term C₃ -C₈ alkenyl is used to represent straight or branched chain hydrocarbon radical which contains three to eight carbons and at least one carbon-carbon double bond, e.g., allyl, while the term C₃ -C₈ alkynyl refers to a straight or branched chain hydrocarbon carbon radical which contains three to eight carbons and at least one carbon carbon triple bond.

The preferred compounds of Formula I are those wherein R is hydrogen; X is cyano; Y is selected from hydrogen, methyl, 2-thienyl, phenyl and phenyl substituted with C₁ -C₄ alkyl, C₁ -C₄ alkoxy or halogen; Z is selected from --C(CN)═, --C(CO₂ C₁ -C₄ alkyl)═, --C(COC₆ H₅)═, --C(SO₂ C₆ H₅)═, --C(SO₂ C₁ -C₄ alkyl)═ and --N═. The preferred colorants are derived by diazotizing these preferred compounds of Formula I and coupling the thus produced diazonium salts with aromatic amine couplers to produce colorants III, wherein R₄ is selected from hydrogen, methyl, halogen, C₁ -C₄ alkoxy and NHCOC₁ -C₄ alkyl; R₅ and R₆ are selected from C₁ -C₄ alkyl and C₁ -C₄ alkyl substituted with hydroxy, C₁ -C₄ alkoxy, C₁ -C₄ alkoxy-C₁ -C₄ alkoxy, cyano, carbamyl, NHCOC₁ -C₄ alkyl, SO₂ C₁ -C₄ alkyl, phenyl, cyclohexyl, C₁ -C₄ alkanoyloxy, C₁ C₄ alkoxycarbonyl, succinimido; cyclohexyl; allyl; R₇, R₈ and R₉ are hydrogen or methyl.

EXPERIMENTAL SECTION Example 1 Preparation of 2-amino-3-carbomethoxy-5-(3-cyanomaleimid-2-yl) thiophene

A solution of 2-chloro 3 cyanomaleimide (0.4 g, 0.0025 m) in ethyl acetate (15 mL) was mixed with a solution of 2-amino 3 carbomethoxythiophene (0.5 g, 0.0025 m) dissolved in ethyl acetate (20 mL) and the reaction mixture stirred for 2 hours. The crystalline dark red colorant thus produced was collected by filtration, washed with ethyl acetate and dried in air (yield-0.5 g, 72% of the theoretical yield). Mass spectrometry supports the following structure: ##STR10##

The colorant has an absorption maximum (λmax) at 526 nm and an extinction coefficient of 17,577 in N,N-dimethylformamide (DMF) solution.

Example 2

To 2-amino-3-carbomethoxy-4-methylthiophene (0.43 g, 0.0025 m) stirred in ethyl acetate (15 mL) was added 2-chloro-3-cyanomaleimide (0.40 g, 0.0026 m) and the reaction mixture heated at reflux for 1.0 hour. The colorant thus produced was collected by filtration, washed with ethyl acetate and dried in air (yield-0.56 g, 76.7% of the theoretical yield). Mass spectrometry supports the following structure: ##STR11##

In the visible absorption spectrum in N,N-dimethylformamide (DMF) an absorption maximum is observed at 531 nm. The colorant has an extinction coefficient of 20,523.

Example 3

2-amino-3-cyano-4-methylthiophene (0.69 g, 0.005 m) and 2-chloro-3-cyanomaleimide (0.80 g, 0.0052 m) were reacted by mixing in ethyl acetate (15 mL) and heating the reaction mixture at reflux for 5 minutes, followed by stirring for one hour while allowing to cool to room temperature. The crystalline product thus produced was collected by filtration, washed with ethyl acetate and dried in air (yield 1.25 g, 96.9% of the theoretical yield). Mass spectrometry supports the following structure: ##STR12##

The colorant when dissolved in CH₂ CH₂ has an absorption maximum at 500 nm and an extinction coefficient (ε) of 19,061.

Example 4

To 2-amino-3-phenylsulfonylthiophene (1.03 g, 0.005 m) stirred at room temperature in ethyl acetate (20 mL) was added 2-chloro-3-cyanomaleimide (0.78 g, 0.005 m) and the reaction mixture heated at 90°-95° C. for 0.5 hour and allowed to cool. The product was collected by filtration, washed with ethyl acetate and dried in air (yield-1.1 g, 61% of the theoretical yield). Mass spectrometry supports the following structure: ##STR13##

In acetone, a visible absorption maximum is observed at 490 nm (ε=26,773) in the visible absorption spectrum.

Example 5

To 2-amino-4-phenylthiazole (3.52 g, 0.02 m) stirred in ethyl acetate (50.0 mL) was added 2-chloro-3-cyanomaleimide (3.12 g, 0.03 m) and the reaction mixture heated at reflux for about 5 minutes and then allowed to cool. The product was collected by filtration, washed with ethyl acetate and dried in air (yield-5.0 g). Mass spectrometry supports the following structure: ##STR14##

An absorption maximum at 526 nm (ε=4,379) is observed in the visible absorption spectrum in methylene chloride.

Example 6

A solution of the dichloromaleimide compound (1.57 g, 0.005)m having the structure: ##STR15## dissolved in N,N-dimethylformamide (10 mL) was treated with 2-amino-3-carbomethoxy-4-methylthiophene (0.86 g, 0.005 m) and then with p toluenesulfinic acid, sodium salt (1.0 g, 0.0056 m) and the reaction mixture stirred at room temperature for 10 minutes and then drowned into water (100 mL) with stirring. The solid product thus produced was collected by filtration, washed with water and dried in air (yield-2.3 g, 80.9% of the theoretical yield). Mass spectrometry supports the following structure: ##STR16##

An absorption maximum is observed at 537 nm (ε_(max) =6,422) in the visible absorption spectrum in methylene chloride.

Example 7

The dichloromaleimide compound (2.36 g, 0.01 m) having the structure: ##STR17## dissolved in 15 mL of acetic acid was reacted with 2-amino-3-carbomethoxy-4-methylthiophene (1.71 g, 0.01 m) and p-toluenesulfinic acid, sodium salt (2.0 g) by stirring the reaction mixture at room temperature for 30 minutes. Isopropanol (50 mL) and then water (100 mL) are added gradually to the reaction mixture with stirring. The product, which is initially oily, crystallizes upon standing for several hours at room temperature and is collected by filtration, washed with water and dried in air (yield-2.9 g, 57.3% of the theoretical yield). Mass spectrometry supports the following proposed structure: ##STR18##

An absorption maximum is observed at 533 nm (ε_(max) =9,459) in the visible absorption spectrum in methylene chloride.

Examples 8 and 9 Diazotization and Coupling

To concentrated sulfuric acid (5.0 mL) was added dry sodium nitrite (0.72 g) portionwise with stirring, while allowing the temperature to rise. After cooling, 1:5 acid (1 part propionic acid: 5 parts acetic acid, v/v) (10 mL) was added at below 5° C. After further cooling, the amine compound of Example 3 (2.58 g, 0.01 m) was added portionwise with good stirring, followed by an additional 15 mL of 1:5 acid, both added at 0.5° C. The reaction mixture was then stirred at 0.5° C. for 2.0 hours. A 0.005 m portion of the diazonium salt solution was added to a chilled solution of 0.005 m of each of the following couplers dissolved in 25 mL of 1:5 acid:

Example 8 3-acetamido-N,N-diethylaniline Example 9 N-ethyl-7-propionamido-1,2,3,4-tetrahydro-2,2,4-trimethylquinoline

Ammonium acetate was added to each of the above coupling mixtures with stirring until they were neutral to Congo Red test paper. After being allowed to couple for 0.5 hour, the blue colorants were precipitated by the addition of water, collected by filtration, washed with water and dried in air. The yield of the colorant of Example 8 was 2.0 g (84.9% of the theoretical yield) and the yield of colorant of Example 9 was 2.2 g (81.4% of the theoretical yield). Each compound was reslurried twice in hot methanol (25 mL), followed by cooling, filtering, washing with methanol and finally drying in air. Mass spectrometry supports the following structures: ##STR19##

In the visible spectra in N,N-dimethylformamide (DMF), the colorant of Example 8 has an absorption maximum (λmax) at 603 nm (ε_(max) -41188), while the colorant of Example 9 has an absorption maximum at 625 nm (ε_(max) -48,038). Tables 1-3 illustrate further the scope of the invention.

                                      TABLE 1                                      __________________________________________________________________________     COMPOUNDS OF FORMULA I                                                          ##STR20##                                                                     Ex.                                                                            No.                                                                               R        X        Y          Z                                              __________________________________________________________________________     10 H        CN       H          C(CN)                                          11 H        CN       C.sub.2 H.sub.5                                                                           C(CN)                                          12 H        CN       C.sub.6 H.sub.4 -4-CH.sub.3                                                               C(CN)                                          13 H        CN       CH.sub.3   C(CONH.sub.2)                                  14 H        CN       H          C(CONHCH.sub.3)                                15 H        CN       H          C(CONHC.sub.4 H.sub.9 -n)                      16 H        CN       CH.sub.3   C(CONHC.sub.3 H.sub.6 OCH.sub.3)               17 H        CN       CH.sub.3   C(CONHC.sub.2 H.sub.4 OH)                      18 H        CN       CH.sub.3   C(CONHC.sub.6 H.sub.11)                        19 H        CN       H          C(CONHCH.sub.2 CHCH.sub.2 )                    20 H        CN       CH.sub.3   C(CONHC.sub.6 H.sub.5)                         21 H        CN       CH.sub.3   C(SO.sub.2 C.sub.6 H.sub.5)                    22 H        CN       H          C(CO.sub.2 C.sub.2 H.sub.4 OC.sub.2                                            H.sub.5)                                       23 H        CN       H          C(CO.sub.2 C.sub.5 H.sub.9)                    24 H        CN       C.sub.6 H.sub.4 -4-OCH.sub.3                                                              C(CO.sub.2 C.sub.2 H.sub.4 OCOCH.sub.3)        25 H        CN       C.sub.6 H.sub.4 -4-Cl                                                                     C(CO.sub.2 CH.sub.2 CHCH.sub.2                 26 H        CN       C.sub.6 H.sub.11                                                                          C(CO.sub.2 CH.sub.2 CH.sub.2 C.sub.6                                           H.sub.5)                                       27 H        CN       C.sub.6 H.sub.10 -p-CH.sub.3                                                              C(CO.sub.2 CH.sub.2 CH.sub.2 OC.sub.6                                          H.sub.5)                                       28 H        CN       C.sub.6 H.sub.3 -3,4-diCl                                                                 C(CO.sub.2 C.sub.6 H.sub.5)                    29 H        SO.sub.2 C.sub.6 H.sub.5                                                                CH.sub.3   C(CN)                                          30 H        SO.sub.2 CH.sub.3                                                                       H          C(CO.sub.2 CH.sub.3)                           31 H        SO.sub.2 C.sub.4 H.sub.9 -n                                                             C.sub.6 H.sub.5                                                                           C(CN)                                          32 H        SO.sub.2 C.sub.6 H.sub.3 -3,4-diCl                                                      H          C(CN)                                          33 H        SO.sub.2 C.sub.6 H.sub.11                                                               CH.sub.3   C(CONHC.sub.2 H.sub.5)                         34 C.sub.2 H.sub.5                                                                         CN       H          C(CN)                                          35 C.sub.6 H.sub.5                                                                         CN       CH.sub.3   C(CN)                                          36 CH.sub.2 CHCH.sub.2                                                                     CN       Cl         C(CN)                                          37 CH.sub.2 C.sub.6 H.sub.5                                                                CN       Br         C(SO.sub.2 CH.sub.3)                           38 CH.sub.2 CH.sub.2 OH                                                                    CN       H          C(CO.sub.2 C.sub.2 H.sub.5)                    39 H        CN       H          C(CO.sub.2 C.sub.8 H.sub.17 -n)                40 H        CN       2-thienyl  C(CN)                                          41 H        CN       5-chloro-2-thienyl                                                                        C(CO.sub.2 CH.sub.3)                           42 H        CN       2-furyl    C(CN)                                          43 H        CN       5-methyl-2-thienyl                                                                        C(CO.sub.2 C.sub.2 H.sub.5)                    44 H        CN       H          N                                              45 H        CN       CH.sub.3   N                                              46 CH.sub.3 CN       C.sub.6 H.sub.5                                                                           N                                              47 C.sub.6 H.sub.11                                                                        CN       C.sub.6 H.sub.4 -4-OC.sub.2 H.sub.5                                                       N                                              48 CH.sub.2 CH.sub.2 C.sub.6 H.sub.5                                                       SO.sub.2 C.sub.6 H.sub.5                                                                C.sub.6 H.sub.5                                                                           N                                              49 H        SO.sub.2 C.sub.6 H.sub.4 -4-Cl                                                          C.sub.6 H.sub.4 -4-Cl                                                                     N                                              50 H        SO.sub.2 C.sub.6 H.sub.4 -2-Br                                                          C.sub.6 H.sub.4 -2-Br                                                                     N                                              51 H        CN       thienyl    N                                              52 H        CN       5-bromo-2-thienyl                                                                         N                                              53 H        CN       furyl      N                                              54 H        CN       5-methyl-2-thienyl                                                                        N                                              55 H        CN       C.sub.6 H.sub.4 -4-C.sub.4 H.sub.9 -n                                                     N                                              56 H        CN       C.sub.6 H.sub.4 -4-NHCOCH.sub.3                                                           N                                              57 C.sub.6 H.sub.4 -4-CO.sub.2 CH.sub.3                                                    SO.sub.2 C.sub.6 H.sub.5                                                                C.sub.6 H.sub.4 -2-OC.sub.4 H.sub.9 -n                                                    N                                              58 C.sub.6 H.sub.4 -4-SO.sub.2 CH.sub.3                                                    SO.sub.2 C.sub.6 H.sub.4 -4-CH.sub.3                                                    C.sub.6 H.sub.4 -4-OH                                                                     N                                              59 H        CN       C.sub.6 H.sub.4 -4-OCOCH.sub.3                                                            N                                              60 CH.sub.2 C.sub.6 H.sub.4 -3-CN                                                          CN       C.sub.6 H.sub.5                                                                           N                                              61 H        CN       CH.sub.3   C[CO.sub.2 CH(CH.sub.3).sub.2 ]                62 H        CN       CH.sub.3   C[CO.sub.2 CH.sub.2 CH(C.sub.2 H.sub.5)C.s                                     ub.4 H.sub.9 n]                                63 H        CN       H          C[CO.sub.2 C.sub.2 H.sub.4 OC.sub.2                                            H.sub.4 OH]                                    64 H        CN       H          C[CO.sub.2 CH(CH.sub.3)]C.sub.2 H.sub.5        65 H        CN       H          C(COC.sub.6 H.sub.5)                           66 H        CN       H          C[COC(CH.sub.3).sub.3 ]                        __________________________________________________________________________

    TABLE 2       COLORANTS OF FORMULA III       ##STR21##       Ex.        No. R X Y Z R.sub.4 R.sub.5 R.sub.6       67 H CN H C(CN) H C.sub.2 H.sub.5 C.sub.2 H.sub.5 68 H CN H C(CO.sub.2      CH.sub.3) 3-CH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.4 OH 69 H CN CH.sub.3 C      (CN) 3-OCH.sub.3 C.sub.4 H.sub.9 -n C.sub.4 H.sub.9 -n 70 H CN CH.sub.3      C(CN) 2-OCH.sub.3 -5-CH.sub.3 H CH(CH.sub.3)C.sub.2 H.sub.5 71 H CN H      C(CO.sub.2 C.sub.2 H.sub.5) 3-Cl CH.sub.2 CH.sub.2 OCOCH.sub.3 CH.sub.2      CH.sub.2 OCOCH.sub.3 72 H CN H C(CO.sub.2 C.sub.4 H.sub.9       -n) 3-NHCOCH.sub.3 C.sub.3 H.sub.7 -n C.sub.3 H.sub.7 -n 73 H CN H      C(CO.sub.2 C.sub.6 H.sub.11) 3-NHCOC.sub.2 H.sub.5 C.sub.2 H.sub.5      CH.sub.2 C.sub.6 H.sub.5 74 H CN C.sub.6 H.sub.5 C(CN) 3-NHCO.sub.2      C.sub.2 H.sub.5 C.sub.2 H.sub.5 C.sub.6 H.sub.11 75 H CN CH.sub.3      C(SO.sub.2 C.sub.6 H.sub.5) 3-NHCOC.sub.6 H.sub.5 C.sub.2 H.sub.5      CH.sub.2 CH.sub.2 OCOC.sub.2 H.sub.5 76 H CN H C(SO.sub.2 C.sub.6      H.sub.5) 3-NHCONHC.sub.6 H.sub.5 C.sub.2 H.sub.5 CH.sub.2 C.sub.6      H.sub.11 77 H CN H C(CO.sub.2 CH.sub.3) 2-OCH.sub.3 -5-NHCOCH.sub.3      C.sub.2 H.sub.5 C.sub.2 H.sub.5 78 H CN H C(CO.sub.2       CH.sub.3) 2,5-di-OCH.sub.3 H C.sub.6 H.sub.11 79 H CN H C(CO.sub.2      CH.sub.3) 3-NHCOCH.sub.2 OH C.sub.2 H.sub.5 C.sub.2 H.sub.5 80 H CN H      C(COC.sub.6 H.sub.5) 3-NHCOCH.sub.3 C.sub.2 H.sub.5 C.sub.6 H.sub.11 81      H CN H C[COC(CH.sub.3).sub.3 ] 3-NHCOCH.sub.3 C.sub.2 H.sub.5 CH.sub.2      CH.sub.2 CN 82 H CN H C(CO.sub.2 C.sub.2 H.sub.5) 3-CH.sub.3 C.sub.2      H.sub.4 OCOCH.sub.3 C.sub.2 H.sub.4       OCOCH.sub.3 83 H CN H C(CN) 3-NHCOCH.sub.3 C.sub.2 H.sub.4 OC.sub.2      H.sub.4  84 H CN H C(CN) H C.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4  85      H CN H C(CN) 3-CH.sub.3 C.sub.2 H.sub.4 N(COCH.sub.3)C.sub.2 H.sub.4  86      H CN H C(CO.sub.2 CH.sub.3) H C.sub.2 H.sub.4 SC.sub.2 H.sub.4   87 H CN C      H.sub.3 C(SO.sub.2 C.sub.6 H.sub.5) 3-NHSO.sub.2 CH.sub.3 C.sub.2      H.sub.5 C.sub.2 H.sub.5 88 H CN CH.sub.3 C(SO.sub.2       CH.sub.3) 3-NHSO.sub.2 C.sub.6 H.sub.5 C.sub.3 H.sub.7 -n C.sub.3      H.sub.7 -n 89 H CN H C(CO.sub.2 CH.sub.3) 3-NHCOCH.sub.3 C.sub.2 H.sub.5      CH.sub.2 CH(OH)CH.sub.2 OH 90 H CN 2-thienyl C(CN) 3-NHCOCH.sub.3      C.sub.2 H.sub.5 CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5 91      H CN 2-furyl C(CN) 3-NHCOC.sub.6 H.sub.11 C.sub.4 H.sub.9 -n CH.sub.2      CH.sub.2 OCH.sub.2 CH.sub.2 OH 92 C.sub.6 H.sub.5 SO.sub.2 C.sub.6      H.sub.5 CH.sub.3 C(CN) 3-NHCOCH(CH.sub.3).sub.2 C.sub.2 H.sub.5 CH.sub.2      CH(OCOCH.sub.3)CH.sub.2 OCOCH.sub.3 93 C.sub.6 H.sub.4 -4-CH.sub.2      CO.sub.2 CH.sub.3 SO.sub.2 C.sub.6 H.sub.4       -4-CH.sub.3 CH.sub.3 C(CO.sub.2 CH.sub.3) 3-NHCOC.sub.2 H.sub.5 C.sub.      2 H.sub.5 CH.sub.2 CH.sub.2 C.sub.6 H.sub.5 94 CH.sub.2 CO.sub.2 C.sub.2      H.sub.5 SO.sub.2 C.sub.6 H.sub.4 -4-CH.sub.3 CH.sub.3 C(CO.sub.2      CH.sub.3) 2-OCH.sub.3 -5-NHCOC.sub.2 H.sub.5 H C.sub.6 H.sub.11 95      C.sub.2 H.sub.5 CN H C(CN) 3-NHCOH C.sub.8 H.sub.17 -n C.sub.8 H.sub.17      -n 96 C.sub.2 H.sub.5 CN H N 3-NHCOCH.sub.3 C.sub.3 H.sub.7 -n C.sub.3      H.sub.7 -n  97 H CN CH.sub.3 N 3-NHCOCH.sub.3 C.sub.2       H.sub.5      ##STR22##        98 H CN C.sub.6 H.sub.5 N 3-NHCOC.sub.2 H.sub.5 C.sub.2 H.sub.5       ##STR23##        99 H CN C.sub.6 H.sub.5 N 3-CH.sub.3 C.sub.2       H.sub.5      ##STR24##        100  H CN C.sub.6 H.sub.5 N 3-CH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.4      OCONHC.sub.6 H.sub.5 101  H CN C.sub.6 H.sub.5 N 3-CH.sub.3 C.sub.2      H.sub.5 C.sub.3 H.sub.6 NHCOCH.sub.3 102  H CN C.sub.6 H.sub.5 N H      C.sub.2 H.sub.5 CH.sub.2 CH.sub.2 CONH.sub.2 103  H CN C.sub.6 H.sub.5 N      3-NHCOCH.sub.3 C.sub.2 H.sub.5 CH.sub.2 CH.sub.2 SC.sub.6 H.sub.5 104  H      CN C.sub.6 H.sub.5 N 3-NHCOC.sub.2 H.sub.5 C.sub.2 H.sub.5 CH.sub.2      CH.sub.2 SC.sub.4 H.sub.9 -n 105  H CN 2-thienyl N 3-CH.sub.3 C.sub.2      H.sub.5 CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2 H.sub.5 106  H CN 2-furyl N      3-CH.sub.3 C.sub.2 H.sub.5 CH.sub.2 CH.sub.2 Cl 107        H CN 5-bromo-2-furyl N 3-CH.sub.3 C.sub.2 H.sub.5 CH.sub.2 CH.sub.2 CN      108  H SO.sub.2 C.sub.6 H.sub.5 C.sub.6 H.sub.5 N 2-Cl H CH.sub.2      CH.sub.2 OH 109  CH.sub.2 CO.sub.2 C.sub.2 H.sub.5 SO.sub.2 C.sub.6      H.sub.4 -4-CH.sub.3 C.sub.6 H.sub.5 N 2-CH.sub.3 H C.sub.2 H.sub.5 110      C.sub.6 H.sub.11 CN C.sub.6 H.sub.5 N 2-Cl-5-OCH.sub.3 CH.sub.2 CH.sub.2      OH CH.sub.2 CH.sub.2 OH 111  H CN C.sub.6 H.sub.4       -4-CH.sub.3 N 3-CH.sub.3 C.sub.2 H.sub.5 CH.sub.2 CH.sub.2 NHSO.sub.2      CH.sub.3 112  H CN C.sub.6 H.sub.4 -4-OCH.sub.3 N 3-CH.sub.3 CH.sub.2      CH.sub.2 OCO.sub.2 C.sub.2 H.sub.5 CH.sub.2 CH.sub.2 OCO.sub.2 C.sub.2      H.sub.5 113  H CN C.sub.6 H.sub.4 -4-Cl N 3-CH.sub.3 C.sub.4 H.sub.9 -n      CH.sub.2 CH.sub.2 Cl 114  H CN C.sub.6 H.sub.5 N 3-NHCOCH.sub.3 C.sub.2      H.sub.5 CH.sub.2 CH(OH)CH.sub.2 OH 115  H CN C.sub.6 H.sub.5 N H C.sub.2      H.sub.5 CH.sub.2 C.sub.6 H.sub.4 -4-CO.sub.2 CH.sub.3  116  H CN C.sub.6      H.sub.11 N H C.sub.2       H.sub.5      ##STR25##        117  H CN C(CH.sub.3).sub.3 N 3-CH.sub.3 C.sub.2       H.sub.5      ##STR26##        118  H CN C.sub.6 H.sub.5 N 3-CH.sub.3 C.sub.2       H.sub.5      ##STR27##        119  H CN C.sub.6 H.sub.5 N 3-C.sub.2 H.sub.5 C.sub.2       H.sub.5      ##STR28##        120  H CN C.sub.6 H.sub.5 N H C.sub.2       H.sub.5      ##STR29##        121  H CN C.sub.6 H.sub.5 N 3-NHCOCH.sub.3 H CH(CH.sub.3)C.sub.4      H.sub.9 -n 122  H CN C.sub.6 H.sub.5 N 3-CH.sub.3 C.sub.2 H.sub.5      CH.sub.2 CH(OH)CH.sub.2 Cl  123  H CN C.sub.6 H.sub.5 N 3-CH.sub.3      C.sub.2       H.sub.5      ##STR30##

    TABLE 3       COLORANTS OF FORMULA III       ##STR31##       Ex.          No. R X Y Z R.sub.4 R.sub.5 R.sub.7 R.sub.8 A       124 H CN H C(CN) 7-NHCOCH.sub.3 C.sub.2 H.sub.5 CH.sub.3 CH.sub.3      CH(CH.sub.3) 125 H CN H C(CN) 7-CH.sub.3 C.sub. 2 H.sub.5 CH.sub.3      CH.sub.3 CH(CH.sub.3) 126 H CN H C(CN) H C.sub.2 H.sub.5 CH.sub.3      CH.sub.3 CH(CH.sub.3) 127 H CN H C(CN) 7-CH.sub.3 C.sub.4 H.sub.9 -n      CH.sub.3 H CH.sub.2  128 H CN H C(CO.sub.2 CH.sub.3) 7-NHCOC.sub.2      H.sub.5 C.sub.2 H.sub.5 CH.sub.3 CH.sub.3 CH(CH.sub.3) 129 H CN CH.sub.3 C      (CO.sub.2 C.sub.2 H.sub.5) 7-CH.sub.3 CH.sub.2 CH.sub.2 OH CH.sub.3 H      CH(CH.sub.3) 130 H CN CH.sub.3 C(CN) H C.sub.4 H.sub.9 -n H H CH.sub.2      131 H CN CH.sub.3 C(CN) 5-CH.sub.3, 8-OCH.sub.3 C.sub.2 H.sub.5 CH.sub.3      H CH.sub.2  132 H CN CH.sub.3 C(CN) 7-CH.sub.3 CH.sub.2 CH.sub.2      CH.sub.2 CONH.sub.2 CH.sub.3 CH.sub.3 CH(CH.sub.3).sub.2  133 H CN      CH.sub.3 C(CN) 7-OCH.sub.3 CH.sub.2 CH.sub. 2 OC.sub.6 H.sub.5 H H      CH.sub.2  134 H CN CH.sub.3 C(CN) 7-CH.sub.3 CH.sub.2 CH.sub.2 SO.sub.2      CHCH.sub.2 CH.sub.3 H CH.sub.2  135 H CN CH.sub.3 C(CN) 7-CH.sub.3      CH.sub.2 CHCH.sub.2 CH.sub.3 H CH.sub.2  136 H CN CH.sub.3 C(CN)      7-OC.sub.2 H.sub.5 CH.sub.2 CH.sub.2 CH.sub.2 SO.sub.2 CH.sub.3 CH.sub.3      H CH.sub.2  137 H CN CH.sub.3 C(CN) H C.sub.2 H.sub.5 H H O 138 H CN      CH.sub.3 C(CN) H C.sub.2 H.sub.4 OCOCH.sub.3 CH.sub.3 H O 139 H CN      CH.sub.3 C(CN) 7-CH.sub.3 CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5 CH.sub.3 H      O 140 H CN H C(CN) 7-NHCOCH.sub.3 C.sub.2 H.sub.5 H H O 141 H CN H C(CN)      7-NHCOC.sub.2 H.sub.5 C.sub.4 H.sub.9 -n CH.sub.3 H O 142 H CN C.sub.6      H.sub.5 N 7-NHCOCH.sub.3 C.sub.2 H.sub.5 CH.sub.3 CH.sub.3 CH(CH.sub.3)      143 H CN C.sub.6 H.sub.5 N 7-CH.sub.3 CH.sub.2 CH.sub.2 OH CH.sub.3      CH.sub.3 CH(CH.sub.3) 144 H CN C.sub.6 H.sub.5 N 7-NHCOCH.sub.3 C.sub.2      H.sub.5 H H O 145 H CN C.sub.6 H.sub.5 N H C.sub.2 H.sub.5 H N * 146 H      CN C.sub.6 H.sub.5 N 7-CH.sub.3 C.sub.2 H.sub.5 CH.sub.3 H * 147 H CN H      C(CN) 7-NHCOCH.sub.3 C.sub.2 H.sub.5 CH.sub.3 H * 148 H CN H C(CO.sub.2      CH.sub.3) 7-CH.sub.3 C.sub.2 H.sub.4 OCOCH.sub.3 CH.sub.3 H * 149 H CN      CH.sub.3 C(CO.sub.2 CH.sub.3) 7-CH.sub.3 C.sub.4 H.sub.9 -n CH.sub.3 H *      150 H CN C.sub.6 H.sub.5 C(CN) H CH.sub.2 C.sub.6 H.sub.11 H H * 151 H      CN H C(COC.sub.6 H.sub.5) 7-CH.sub. 3 CH.sub.2 CH.sub.2 C.sub.6 H.sub.5      H H * 152 H CN H C(COC.sub.6 H.sub.5) 7-NHCOCH.sub.3 CH.sub.2       CH(CH.sub.3).sub.2 CH.sub.3 CH.sub.3 CH(CH.sub.3) 153 CH.sub.2 CO.sub.2      C.sub.2 H.sub.5 SO.sub.2 C.sub.6 H.sub.5 CH.sub.3 C(CO.sub.2 CH.sub.3)      7-NHCOCH.sub.3 H CH.sub.3 CH.sub.3 CH(CH.sub.3) 154 CH.sub.2 CO.sub.2      C.sub.2 H.sub.5 SO.sub.2 C.sub.6 H.sub.5 CH.sub.3 C(CO.sub.2 CH.sub.3)      7-CH.sub.3 C.sub.2 H.sub.5 CH.sub.3 CH.sub.3 CH(CH.sub.3) 155 C.sub.6      H.sub.5 CN CH.sub.3 C(CN) 7-CH.sub.3 CH.sub.2 CH.sub.2 NHCOCHCH.sub.2 H      H CH(CH.sub.3) 156 C.sub.6 H.sub.5 CN CH.sub.3 C(CN) 7-CH.sub.3 CH.sub.2      CH(OH)CH.sub.2 OH CH.sub.3 H CH.sub.2  157 C.sub.2 H.sub.5 CN H C(CN)      7-CH.sub.3 CH.sub.2 CN(OH)CH.sub.2 OH CH.sub.3 H O 158 H CN CH.sub.3      C(CN) 7-CH.sub. 3 CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5      CH.sub.3 H OH(CH.sub.3) 159 H CN CH.sub.3 C(CN) 7-CH.sub.3 CH.sub.2      CH.sub.2 OCH.sub.2 CH.sub.2 CN CH.sub.3 H O 160 H CN CH.sub.3 C(CN)      7-CH.sub.3 CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH CH.sub.3 H CH.sub.2      161 H CN H C(CN) H CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OCOCH.sub.3 H H      CH.sub.2  162 H CN 2-thienyl C(CN) H CH.sub.2 CH.sub.2 CN CH.sub.3 H      CH.sub.2  163 H CN 2-thienyl N 7-NHCOCH.sub.3 C.sub.2 H.sub.5 CH.sub.3      CH.sub.3 CH(CH.sub.3)       164 H CN 2-furyl N 7-CH.sub.3      ##STR32##       H H CH.sub.2   165 H CN 5-chloro-2- N 7-CH.sub.3 CH.sub.2 CH.sub.2      SO.sub.2 CH.sub.2 CH.sub.2 SC.sub.6 H.sub.5 CH.sub.3 H CH.sub.2      thienyl  166 H CN C.sub.6       H.sub.5 N 7-CH.sub.3      ##STR33##       CH.sub.3 H O  167 H CN C.sub.6 H.sub.5 N 7-CH.sub.3 CH.sub.2 CH.sub.2      SO.sub.2 NH.sub.2 CH.sub.3 H O 168 H CN C.sub.6 H.sub.5 N 7-CH.sub.3      CH.sub.2 CH.sub.2 SO.sub.2 N(C.sub.2 H.sub.4 OH).sub.2 CH.sub.3 H      CH.sub.2  169 H CN C.sub.6 H.sub.5 N 7-CH.sub.3 CH.sub.2 CH.sub.2      CH.sub.2 NHSO.sub.2 CH.sub.3 CH.sub.3 H CH.sub.2  170 H CN C.sub.6      H.sub.5 N 7-NHCOC.sub.6 H.sub.5 C.sub.2 H.sub.5 CH.sub.3 CH.sub.3      CH(CH.sub.3) 171 H CN C.sub.6 H.sub.5 C(CN) 7-NHCO.sub.2 C.sub.2 H.sub.5      C.sub.8 H.sub.17 -n H H CH.sub. 2  172 H CN H C(CN) 7-NHCOC.sub.6      H.sub.5 C.sub.4 H.sub.9 -n CH.sub.3 H CH.sub.2   173 H CN H C(CN)      7-NHCOC.sub.6       H.sub.11      ##STR34##       CH.sub.3 H CH.sub.2   174 H CN H C(CO.sub.2 CH.sub.3) 7-NHSO.sub.2      CH.sub.3       ##STR35##       CH.sub.3 H CH.sub.2   175 H SO.sub.2 CH.sub.3 H C(CN) 7-NHCONHC.sub.2      H.sub.5 CH.sub.2 CH.sub.2 OC.sub.2       H.sub.5 CH.sub.3 CH.sub.3 CH(CH.sub.3) 176 H CN H C(CN) 7-Cl C.sub.2      H.sub.5 CH.sub.3 H CH.sub.2      *The asterisk is used to represent a covalent bond to form an indoline      ring. 

We claim:
 1. A compound of the formula: ##STR36## wherein R is hydrogen; C₁ -C₈ alkyl; C₁ -C₈ alkyl substituted with at least one group selected from the list consisting of halo, hydroxy, C₁ -C₆ alkoxy, C₁ -C₆ alkanoyloxy , C₅ -C₇ cycloalkyl, cyano, C₁ -C₆ carbalkoxy, phenyl, phenyl substituted by one or two groups selected from the list consisting of C₁ -C₆ alkyl, C₁ -C₆ alkoxy, C₁ -C₆ alkoxycarbonyl, C₁ -C₆ alkanoyloxy, C₁ -C₆ alkanoylamino, halo, cyano, C₁ -C₆ alkylsulfonyl, and hydroxy, phenoxy, phenoxy substituted with one or two groups selected from the list consisting of C₁ -C₆ alkyl, C₁ -C₆ alkoxy, C₁ -C₆ alkoxycarbonyl, C₁ -C₆ alkanoyloxy, C₁ -C₆ alkanoylamino, halo, cyano, C₁ -C₆ alkylsulfonyl, and hydroxy, or R is C₃ -C₈ alkenyl; C₃ -C₈ alkynyl; C.sub. 5 -C₇ cycloalkyl, C₅ .C₈ cycloalkyl substituted with one or two groups selected from the list consisting of C₁ -C₄ alkyl, C₁ -C₄ alkoxy, hydroxy, and C₁ -C₄ alkanoyloxy; phenyl; or phenyl substituted by one or two groups selected from the list consisting of C₁ -C₆ alkyl, C₁ -C₆ alkoxy, C₁ -C₆ alkoxycarbonyl, C₁ -C₆ alkanoyloxy, C₁ -C₆ alkanoylamino, halo, cyano, C₁ -C₆ alkylsulfonyl, and hydroxy;X is cyano, C₁ -C₈ alkylsulfonyl, phenylsulfonyl, or phenylsulfonyl substituted by one or two groups selected from the list consisting of C₁ -C₆ alkyl, C₁ -C₆ alkoxy, C₁ -C₆ alkoxycarbonyl, C₁ -C₆ alkanoyloxy, C₁ -C₆ alkanoylamino, halo, cyano, C₁ -C₆ alkylsulfonyl, and hydroxy; Y is hydrogen, C₁ -C₄ alkyl; C₅ -C₇ cycloalkyl; halogen; phenyl; phenyl substituted by one or two groups selected from the list consisting of C₁ -C₆ alkyl, C₁ -C₆ alkoxy, C₁ -C₆ alkoxycarbonyl, C₁ -C₆ alkanoyloxy, C₁ -C₆ alkanoylamino, halo, cyano, C₁ -C₆ alkylsulfonyl, and hydroxy; 2-thienyl; 2-thienyl substituted with one of two halogen C₁ -C₄ alkyl, or C₁ -C₄ alkoxy, or Y is 2-furanyl; Z is nitrogen or a group of the formula --C(R₁) ═, wherein R₁ is cyano, --CO₂ R₂, --COR₃, --CONHR₂, or --SO₂ R₃, wherein R₂ is hydrogen; C₁ -C₈ alkyl; C₁ -C₈ alkyl substituted with at least one group selected from the list consisting of halo; hydroxy; C₁ -C₆ alkoxy; C₁ -C₆ alkanoyloxy; C₅ -C₇ cycloalkyl; cyano; C₁ -C₆ carbaloxy; phenyl; phenyl substituted by one or two groups selected from the list consisting of C₁ -C₆ alkyl, C₁ -C₆ alkoxy, C₁ -C₆ alkoxycarbonyl, C₁ -C₆ alkanoyloxy, C₁ -C₆ alkanoylamino, halo, cyano, C₁ -C₆ alkylsulfonyl, and hydroxy, phenoxy; and phenoxy substituted with one or two groups selected from the listing consisting of C₁ -C₆ alkyl, C₁ -C₆ alkoxy, C₁ -C₆ alkoxycarbonyl, C₁ -C₆ alkanoyloxy, C₁ -C₆ alkanoylamino, halo, cyano, C₁ -C₆ alkylsulfonyl, and hydroxy; or R₂ is C₅ -C₇ cycloalkyl; C₃ -C₈ alkenyl; phenyl; or phenyl substituted by one or two groups selected from the list consisting of C₁ -C₆ alkyl, C₁ -C₆ alkoxy, C₁ -C₆ alkoxycarbonyl, C₁ -C₆ alkanoyloxy, C₁ -C₆ alkanoylamino, halo, cyano, C₁ -C₆ alkylsulfonyl, and hydroxy; and R₃ is C₁ -C₈ alkyl; phenyl; or phenyl substituted by one or two groups selected from the list consisting of C₁ -C₆ alkyl, C₁ -C₆ alkoxy, C₁ -C₆ -alkoxycarbonyl, C₁ -C₆ alkanoyloxy, C₁ -C₆ alkanoylamino, halo, cyano, C₁ -C₆ alkylsulfonyl, and hydroxy.
 2. The compound of claim 1, wherein R is hydrogen.
 3. The compound of claim 1, wherein R is hydrogen; X is cyano; Y is hydrogen, methyl, or phenyl, and Z is --N═.
 4. The compound of claim 1, wherein R is hydrogen; X is cyano; Y is hydrogen, methyl, or phenyl; and Z is --C(CO₂ C₁ -C₈ alkyl)═ or --C(CN)═.
 5. The compound of claim 1 having the formula ##STR37##
 6. The compound of claim 1 having the formula ##STR38##
 7. The compound of claim 1 having the formula ##STR39##
 8. The compound of claim 1 having the formula ##STR40##
 9. The compound of claim 1 having the formula ##STR41## 